acid and alkyl iodide. The primary amine is decomposed with
HNO.,, forming the alcohol, and nitrogen is evolved,
CJlr.NIlo I UNO., - GUI../'.)!!: -I- No -[- II.O.
The secondary amine forms the nitrosamine, insoluble in water
(Coiy,NII | UNO.,- (C.II-^N.NO -1-II.p.
The tertiary amine is unacted on by nitrous acid, but, unlike
the other two, unites with an alkyl iodide and forms the
quaternary ammonium iodide (I lofmann),
(<UIr,):,N I- CH:1I --- (Coirs):,NCIT,,T.>
The behaviour of nitrous acid with the aromatic amines is
somewhat different (See Preps. 60, p. 157, and 62, p. 161).
The primary amines may also be distinguished from second-
ary and tertiary amines by the isocyanide reaction (p. 150), which
consists in heating the amine with a Itttle chloroform and alco-
holic potash solution. An intolerable odour of isocyanide is
Coilr.NHo 1- CIICL. -I- 3KOIT ™ C«MflNC + 3KC1 + 3lU).
PREPARATION 15. Ill3
Ethyl Acetate. —Esters may be obtained by the direct action
of the alcohol on the acid as in the case of methyl oxalate.
(Prep 26, p. roi). A certain quantity of ethyl acetate is also
obtained from ethyl alcohol and acetic acid, '-but the action, which
is a reversible one, stops when a certain proportion of the con-
stitucnts have (-ombined (p. 234). It is represented thus :
c,n,()ir i c:n:,.(:oon^;cii3.coocviB + n,o, /,
which signifies that the ester and water react and regenerate f^
alcohol and acid, whilst the reverse process is in operation. P>y
removing the water as it is formed by means of sulphuric acid
or by distillation, this condition of equilibrium is disturbed and
the reaction is completed. This does not, however, explain the
fact, first discovered by Scheele and afterwards investigated by
Fischer and Speier (see Prep. 99, p. 209), that a very limited f\
quantity of cone, sulphuric or hydrochloric acid will produce fe '